Explosive and process of making explosives



s'rnrss .mcon BARAB, or FLUSHING, NEW YORK, nss enon TO THE COMMERCIALnnsn gn COMPANY, or LONG ISLAND CITY, NEW YORK, A CORPORATION OF NEWYORK.

when used in either the dynamite or col- EXPLOSIVE AND PROCESS OFMAKING- EXPLOSIVES.

No Drawing.

Application filed July 14,

T 0 all whom it may concern: Be it known that I, J ACQB BARAB, a citizenof the United States, residing at Flushing, county ofQueens, and Stateof New. York, have rinvented certain new and useful Imfi'ovements inExplosives and Processes of aking Explosives, fully described andrepresented in the following specification. I The present inventionrelates to new explosives and to processes of making ex-- plosives, I

It has been recognized that nitro-glycerin used in its liquid state hasvery valuable properties as an explosive, but it has some disadvantagesthat are .so serious as to materially restrict its employment in theliquid state, and even to injuriously affect its value loidal forms. I

The principal disadvantages of nitroglycerin and explosive mixturescontaining it are that-they freeze at a commonly occurring lowatmospheric temperature (6. 9.

pure nitro-glycerin melts at 133 C.) and that they are relativelysensitive to friction and shock. At high temperatures (180 to 200 C.)liquid nitro-glycerin explodes.

As a result of these disadvantageous properties, the use of the liquidnitro-glycerin in explosives is restricted to those cases where theliquid condition, theqquick action,and

great strength are so important as to override the dangers due to thedisadvantageous properties.

In its broad aspect thepres'ent invention comprises an explosive whichwill remain liquid at all atmospheric temperatures encountered in actualpractice, which'will be insensitive to friction, relatively insensitiveto shock, which will-not decompose at, and also will be sufficientlynonvolatile at atmospheric temperatures to be satisfactory for practicalpurposes. Furthermore, whendetonated by a primer, it will be as quickglycerin.

Such an explosive has all the advantages of liquid nitro-glycerinwithout its dangerous disadvantages. 1 I The starting material for thenew explosive is a propylene glycol product, such, for example, asismade from oil gas by selecin action and fully as strong as nitrotivelychlorinating the oil gas to form mostly Specification of Letters Patent;

,sive having still further liquid explosive which 1 Patented Mar. 15,1921.

Byron E. ldred, filed July 3, 1917.

This particular glycol when-suitably nitrated and properlystabilizedgivesi an explosive product which has the propertieshereinbefore recited. On analysis, it has substantially thepercentagecomposition of propylene glycol dinitrate, although its physlcalproperties, stated above, particuand then converting plication SerialNo. 178,364 to I larly distingulsh it as an explosive from.

any nitrated glycols heretofore known to me.

Wh1le an explosive having the above recited properties is practice, itispossible in the best embodiment of the invention to provide anexploproperties.

F or example, I have produced,

highly advantageous in very advantageous as a specific embodiment of theinvention, a I

shown by the following:

It requires more than sixty minutes produce the standard coloration onstand ard potassium iodid starch papers at 71 C., as employed in theAbel heat tests 1 A drop of this liquid explosive at the end had theproperties of a capillary tube, when suddenly introduced into a hotflame merely without exploding.

When subjected to continuous heating with gradually risingtemperature,.under atmospherie pressure, there was no, visibledecomposition until about 1409 C. Above this temperature, up to 200 (3.,the product volatilized with decomposition, but at no time decomposesduring this heating did it decompose with explosive violence.

i A few 0. c., in a test tube heated over a candle flame entirelyvolatilized with decomposition, but at no time did it reach explosiveviolence.

It willwithstand a temperature of ,40 Crwithout freezing.

When subjected to atemperature of 50 C. for fifteen to twenty minutes,it becomes somewhatthick or more viscous, but does not become solid andquickly returns to its" normal condition with increase of temperature.

The new product is non-hygroscopic and insensitive to friction. It ismore insensitive to shdck than nitroglycerin, but can be detonated by arelatively weak primer and the detonation appears to be as quick andcomplete as with nitroglycerin, for tests of the new explosive in bothopen and closed,

without exploding it or even igniting theexplosive.

A commerclal nitroglycol made in accordance with the present invention,had a light straw color, and a specific gravity of 1.38 at 23 C. Onanalysis, it gave 16.73 per cent. nitrogen. i

From the above-mentioned new liquid explosive, a new solid explosiveproduct may be formed. This consists of a mixture of the liquidexplosive with a suitable absorbent. In one embodiment of the inventionwhich gave good results, this solid explosive product was made bycombining 40 per cent. of. the liquid explosive with 4 1 per cent.sodium nitrate, 15 per cent. of wood pulp and 1 per cent. calciumcarbonate.

This new solid explosive mixture was submitted to centrifugal action forfive minutes at a rate of six hundred revolutions per minute: The lossof the explosive liquid due to this action, was only two and one-half.

per cent. This is well within the limit of safety. 1

The new explosive product has beenkept in a loosely covered ca sule fortwo days in a heated oven at 75 with a loss due to volatilization ofonly 3 per cent., and test of the vapor showed no products ofdecomposition. J

This new explosive in-sol'id form when detonated was found to" besomewhat more powerful than aetO per cent. dynamite made steel anvil,the new explosive in solid form did not explode and no indication oflocal cracking produced by the explosive could be noted, even when thependulum was dropped from a height of 2 meters.

The corresponding, nitroglycerin dyna mite tested in the same machineexploded every time, even when the pendulum was dropped from a height ofonly 1 meters.

pheric temperatures, nor temperatures up to m practically insensitive tofriction; does not freeze at any atmospheric temperatures, nor anytemperatures down to 50 C. and at very high temperatures decomposeswithout exploding. The sensitiveness to shock of the new explosive maybe still further reduced by the addition of camphor, as itsatisfactorily responds to the latter treatment.

An explosive gelatin was made up as follows: l la parts ofnitrocellulose (showing 12.25% nitrogen), 100 parts of nitratedpropylene glycol. This formed a very stiff consistent gel, which understrong pressure and continued standing, showed-no signs of exudation.This gel easily detonated when. a primer containing three-tenths of agram of fulminate of mercury was used. In the Trauzl lead. block test itproduced an expansion of 420 c. c. Picric acid, as well astrinitrotoluol, under similar conditlons, produced an expansion of about215 c. c.

. The new process for the manufacture of the new liquid explosivehereinbefore referred to, will now be described.

While this process when applied to the nitration of a propylene glycolof the kind hereinbefore. designated results in the valuable liquidexplosive described, it is to be understood that this part of theinvention is not limited to the use of such propylene glycol, but givesan improved nitrated product when other glycols such as those ofethylene or the butyle'nes are used as a starting material. For example,although nitrated ethylene glycol has been made heretofore by otherprocesses, it has not been C.; is much less sensitive to shock; is

satisfactory for explosive purposes, because of its high volatility andinstability under atmospheric conditions.

When, however, it is made in accordance with the present invention, theresultant product, although still somewhat volatile, 1s

much less so than by the old process. Moreover, the glycols whennitrated and stabilized'in accordance" with the present invention willendure the Abel heat test at71 C., a much longer time than. when madeby' three minutes takes'place.

previous processes.

The method of nitrating will now be described in its preferred form asapplied to the nitration of a propylene glycol, and particularly thepropylene glycol obtained as hereinbefore described.

The composition of the acid mixture used for nitrating the glycols mayvaryv greatly; for example:

Water from 0 to 15% Nitric acid 25 to 50% I i Sulfuric acid 50 to 70%.

The quantity of acid used for the nitration is calculated so that fromeight to ten per cent. of nitric acid will remain in the spent acid.

f One of the acid mixtures used for nitrating was of approximately thefollowing composition, by weight: E

Sulfuric acid 01.00 Nitric acid 36.00% Water 3.00%

mixture, which is kept well stirred, prefer-' ably byair agitation.

After all the glycol is added the mixture is allowed to stand for ashort time, usually about ten minutes, at a temperature not-exwashingtreatment.

ceeding 1 0 C- On standing, the nitrated glycol separates readily fromthe acid mixture and rises to the top. The acid mixture is removed, forexample, by drawing itofhfrom the bottom, and then the nitrated glycolis subjected to a The first washing is done very thoroughly with wateruntil a test with litmus paper shows the'nitrated product to be aboutneutral. Usually about four washings of water are required, each lastingthree to five minutes, carried out with air agitation' After suflicientwashing with water to obtain the desired neutrality, the water beingdecanted from the nitrated product, the latter is then' thoroughlyagitated for a few minutes with about an equal weight of a.

one-fourth per cent. ammonia solution for three minutes.

Then, after the removal of the ammonia wash solution, another washingwith water for about three minutes is given.

Then the nitrated product is washed with a stronger ammonia solution,viz., one containing about one-half'per cent. ammonia -for threeminutes. Then another washing with water follows for three. minutes.Then another, washing with a half per cent. of

ammonia solution for five minutes is given. After this, another washingwith water for four'washes for three to five minutes each.

A It will be noted that this washing method involves the use of plainwater and ammonia solution in alternation; also, the ammonia solution ofthe different ammonia washes is increased in strength, a weaker solutionbeing used at first and a stronger solution being used last. r When theammoniasolution is of the same strengthas the one previously used, thetime of treat ment is increased. In each case the quantityof wash isabout equal in weight to the nitrated product.

The steps recited above are given as best examples for a particularquality of propylene gycol and for the specified acid used. At the sametime it is to be understood that the number of alternate washings may bemodified depending'on the quality of the glycol, the composition of themixed acid and the temperature of nitration. Also, the

strengths of the respective ammonia solutions may be somewhat'modified,it being important, however, to begin the ammonia treatment with theweaker solution and to end it with the stronger solution After thiswashing treatment along the lines indicated, and the last-mentionedthorough Washing with water, the .nitrated product is then suitablydried. In the laboratory this is best carried out in a vacuum desiccatorover calcium chlorid, in the well known manner, for removal of thelasttraces of water. After this drying treatment the product is allowed tostand for a considerable time, usually about six days.

After this agingtreatment the product 1s again subjected to washingsteps,-preferably by first washing with water for three minutes, thenwith a one per cent. ammonia solution for three minutes, again withwater 4 for three minutes, and then with a two per cent. ammoniasolution for five minutes, afterwhich the product is thoroughly washedwith water four or five times for three to five minutes at a wash.

After this, the product is Washed with a borax solution, which should beof about two per cent. strength, for about five minutes. I

Finally, the product is washed with water for about five minutes, andthen is dried in the vacuum desiccator, asbefore. This giv th liquid,explosive product. When theipropylene glycol hereinbefore described isemployed as a starting material, the resultant explosive product willhave the valuable properties hereinbefore described.

One important feature of, the new liquid explosive is that it requires,less nitric acid to nitrate its starting material than doesnitroglycerin. In general terms, itmay be said that nitroglycerinrequires 24% -more nitric acid for'its' nitration than does the,

new liquid.

What is claimed is:

1; An explosive, liquid at all atmospheric: temperatures, andinsensitive t'ofriction' in the, standard pendulum testing, machine,substantially as described, said explosive comprising an olefin glycoldinitrate.

2. An explosive, liquid at all atmospheric temperatures, insensitive tofriction in the standard pendulum testing machine, substantially asdescribed, and whichexplosive is non-hygroscopic, saidcxplosivecomprising an olefin glycol dinitrate. I

3. An explosive, liquid at all atmospheric temperatures insensitive tofriction in the standard pendulum testing machine, ,substantially asdescribed, and when detonated I having substantiallythe sti'ength ofnitroglycerin, said explosive comprising an ole-- fin glycol dinitrate.

'4. The, new explosive product which has substantially the percentagecomposition'of' I propylene glycol dinitrate, which is nonhygroscopic,endures the Abel heat test at. 71 C. for more than an hour, whichdecomposes 'onlvabove 140 C., freezes below -40 C., and a drop of whichwhen suddenly in v troduced into a flame decomposes without exploding. Ii

-5.- An explosive in solid form, comprising an absorbent 'and'a liquidexplosivehaving substantially the percentage composition of minute.

a nitrated propylene glycol, said solid explosive being non-freezing andnon-decomposing at atmospheric temperatures, and losing not to exceed 3,per cent. by weight on centrifuging at 600 revolutions per '6. Anexplosive in solid form, comprising an absorbent and a liquid explosivehaving substantially the percentage composition of a nitrated propyleneglycol, said solid explosive being non-freezing and non-decomposing atatmospheric temperatures, which loses not more than 3 per cent. of itsweight on heating for 48 hours at 75 C., and losing trifuging at 600revolutions per minute.

7. A colloidal explosive comprising nitrocellulose and a liquidexplosive having substantially the percentage composition of propyleneglycol dinitrate.

8. Thenew explosive which has substantially the percentage compositionofpropylene, glycol dinitrate, said explosive being liquid atall'atm'ospheric temperatures and not'to exceed? per cent. by Weight onceninsensitive to friction in the standard pendulum testing machine,substantially as described.

9. The process of producing nitrated glycols,*which' consists insubjecting the glycol to the action of a mixture comprising nitric andsulfuric acids, then washing the ni trated product alternately withwater and with ammonia solutions, and drying it. I 10. The process ofproducing nitrated or-' anic compounds, which consists in subjectmg thecompound to be nitrated to the action of a mixture comprisingn-itric andsulfuric acids, then washing and drying the nitrated product, then agingit, and again washing and drying it after, such aging.

11. The ,step in the process of nitrating glycols, which consists insubjecting the glycol to the action of a mixture comprising nitric andsulfuric acids, washing the n1- product to the action of a solution ofborax,

and then washing and drying it.

12. The-process of producing nitrated ori ganic compounds, whichconsists in sub- Y employed being weakest at first and strongest at theend, thoroughly washing the nitrated product with water, and drying it.

In testimony whereof I have hereunto set my hand.

JACOB BARAB.

,trated product, and finally subjecting the

